主/客配位笼状超分子的激发态动力学:可见光驱动的核/壳电荷转移
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- 英文论文题名：Photophysical Properties of a Post-Self-Assembly Host/Guest Coordination Cage:Visible Light Driven Core-to-Cage Charge Transfer
- 论文作者：杨阳 ; 韩克利
- 英文论文作者：Yang Yang ; Ke-Li Han ; State Key Laboratory of Molecular Reaction Dynamics ; Dalian Institute of Chemical Physics ; Chinese Academy of Sciences
- 年：2016
- 作者机构：中国科学院大连化学物理研究所;
- 论文关键词：激发态光物理动力学 ; 金属有机超分子 ; 瞬态吸收和发射光谱
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第四十四分会：化学动力学
- 语种：中文
- 分类号：O641.3
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第四十四分会 ; 化学动力学
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：240k
- 原文格式：D
- 会议级别：全国
摘要
三维超分子具备独特的光物理特性,它在光医疗,光能源,非线性光学等领域具有潜在的应用价值。利用分子自组装技术,我们使用主体外壳(三维金属有机笼状分子)封装客体内核(光敏剂晕笨)形成了一种主/客配位超分子,利用多时间尺度分辨的超快光谱技术结合量子化学计算,我们发现这种超分子光谱学性能较之晕笨有了极其明显的变化:可见光区的吸光度增强5-6倍,激发态寿命延长至3倍。理论分析认为:客体晕笨分子电荷向主体笼子的迁移导致了可见光区的吸收增强,主体笼子抑制了内核光敏剂的激发态失活途径,该超分子的光物理激发态全过程得到了阐释。本研究提供了一种优化光敏剂的策略。
We report that the encapsulation of a chromophore by a metallacage dramatically enhances its photophysical properties. The encapsulated photosensitizer achieves a 6.5-fold enhancement to its absorptivity. The triplet lifetime of the encapsulated photosensitizer is three times longer than that of its free analogue. These enhancements are attributed to two key factors:(i) encapsulation-induced core-to-cage charge transfer(CCCT) generates new visible-light absorbing states, accounting for the enhanced absorption, and(ii) the microenvironment inside the metallacage inhibits nonradiative decay processes, resulting in prolonged triplet lifetime. This work provides insight into CCCT phenomenon.
We report that the encapsulation of a chromophore by a metallacage dramatically enhances its photophysical properties. The encapsulated photosensitizer achieves a 6.5-fold enhancement to its absorptivity. The triplet lifetime of the encapsulated photosensitizer is three times longer than that of its free analogue. These enhancements are attributed to two key factors:(i) encapsulation-induced core-to-cage charge transfer(CCCT) generates new visible-light absorbing states, accounting for the enhanced absorption, and(ii) the microenvironment inside the metallacage inhibits nonradiative decay processes, resulting in prolonged triplet lifetime. This work provides insight into CCCT phenomenon.
引文
[1]Yang Yang,Jun-Sheng Chen,Jian-Yong Liu,Guang-Jiu Zhao,Lei Liu,Ke-Li Han*,Timothy R.Cook,Peter J.Stang*J.Phys.Chem.Lett.2015,6,1942-1947.